TWI637988B - 經塗佈ptfe膜 - Google Patents
經塗佈ptfe膜 Download PDFInfo
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- TWI637988B TWI637988B TW105117024A TW105117024A TWI637988B TW I637988 B TWI637988 B TW I637988B TW 105117024 A TW105117024 A TW 105117024A TW 105117024 A TW105117024 A TW 105117024A TW I637988 B TWI637988 B TW I637988B
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- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 56
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 55
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 84
- 239000012530 fluid Substances 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- 229920003937 Aquivion® Polymers 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- -1 sulfur peroxide Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 22
- 150000002739 metals Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012930 cell culture fluid Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000011146 sterile filtration Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/08—Polysulfonates
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- B01D2323/08—Specific temperatures applied
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2323/08—Specific temperatures applied
- B01D2323/081—Heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2325/00—Details relating to properties of membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
Abstract
本發明揭示一種非交聯PFSA塗佈之多孔PTFE膜。
Description
本發明係關於經塗佈PTFE膜。
PTFE膜,尤其膨脹式PTFE(expanded PTFE;ePTFE)膜,用於多種液體及氣體過濾應用中,包括涉及處理複雜流體(諸如腐蝕性或化學活性液體)的應用。然而,需要展現金屬清除效率或金屬移除效率同時提供低流阻之多孔PTFE膜。
本發明之此等及其他優點將自如下所闡述之描述顯而易見。
本發明之一具體實例提供一種包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(perfluorosulfonic acid;PFSA)聚合物之非交聯塗層,其中該膜之CWST為至少約30達因/公分(約30×10-5N/cm)。
在另一具體實例中,提供一種用於過濾含金屬流體之方法,該方法包含使含金屬流體穿過包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,其中該膜之CWST為至少約30達因/公分(約30×10-5N/cm),且將金屬自該流體移除。
在另一具體實例中,提供一種用於過濾過氧化硫混合物
(sulfuric perioxide mixture;SPM)流體之方法,該方法包含使該流體穿過包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,其中該膜之CWST為至少約30達因/公分(約30×10-5N/cm),且將粒子自該流體移除。
亦根據本發明之具體實例提供包括該等膜之裝置以及製造該等膜之方法。
圖1為展示與未經處理之PTFE膜及市售UV處理之PTFE膜相比較,根據本發明之PFSA塗佈PTFE膜之各個具體實例的金屬吸收的圖式。
圖2為展示與未經處理之PTFE膜相比較,根據本發明之PFSA塗佈PTFE膜之各個具體實例的金屬吸收的圖式,其展示吸收係歸因於塗佈而非篩分。
根據本發明之一具體實例,多孔PTFE膜包含多孔PTFE基板,其具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,其中該膜之CWST為至少約30達因/公分(約30×10-5N/cm)。
一種用於過濾根據本發明之一具體實例之含金屬流體的方法包含使含金屬流體穿過包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,其中該膜之CWST為至少約30達因/公分(約30×10-5N/cm),且將金屬自該流體移除(例如將第2族金屬(例如Mg及/或Ca)、多價金屬及/或過渡金屬(例如Cr、Mn、
Fe及/或Ni)自該含金屬流體移除)。
在另一具體實例中,提供一種用於過濾過氧化硫混合物(SPM)流體之方法,該方法包含使該流體穿過包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,其中該膜之CWST為至少約30達因/公分(約30×10-5N/cm),且將粒子(諸如含二氧化矽粒子)自該流體移除。
在一具體實例中,提供一種製造金屬移除膜之方法,該方法包含用包含全氟磺酸(PFSA)聚合物之塗層塗佈多孔PTFE基板,且在低於250℃,較佳地低於約200℃之溫度下固化該塗層。
在又一具體實例中,提供一種製造金屬移除膜之方法,該方法包含用包含全氟磺酸(PFSA)聚合物之塗層塗佈多孔PTFE基板,其中不使用交聯劑,且該塗層在室溫下製備;且在低於250℃之溫度下固化該塗層。較佳地,固化在約25℃至約200℃之溫度下進行。
有利地,相比於製備用於一些應用之膜(其中使用金屬劑且藉由後洗滌方法(例如使用HCl)移除金屬劑以滿足標準(例如在微電子工業中)),根據本發明之膜可用不含金屬劑之塗層製備。另外,可在製造友好方法中根據本發明製備膜,例如製備可容易地併入至現有製造方法中,從而提高製備速度。
根據本發明之經塗佈多孔PTFE膜有利地提供高金屬清除效率或金屬移除效率與低流阻之組合,同時在所處理之流體中保持潤濕(亦即,膜在製程流體中為非抗濕潤的),且適用於廣泛範圍之液體及氣體(包括空氣)過濾應用,包括無菌過濾應用。例示性應用包括例如:診斷應用
(包括例如樣本製備及/或診斷側流裝置);噴墨應用;微影,例如作為基於HD/UHMW PE之介質的替代物;流體過濾以用於醫藥工業;金屬移除;超純水製備;工業及表面水之處理;過濾流體以用於醫療應用(包括家庭及/或病患使用,例如靜脈內應用,亦包括例如過濾諸如血液之生物流體(例如,病毒移除));過濾流體以用於電子工業(例如過濾微電子工業中之光阻流體及熱過氧化硫混合物(SPM)流體);過濾流體以用於食品及飲料工業;啤酒過濾;澄清;過濾含抗體及/或蛋白流體;過濾含核酸流體;細胞偵測(包括原位);細胞捕獲;及/或過濾細胞培養流體。替代地,或另外,根據本發明之具體實例之多孔膜可用於過濾空氣及/或氣體,及/或可用於排氣應用(例如允許空氣及/或氣體穿過但不允許液體穿過其間)。根據本發明之具體實例之多孔膜可用於多種裝置中,包括手術裝置及產品,諸如眼科手術產品。本發明膜為在尺寸上穩定的。在一些具體實例中,多孔PTFE膜可個別地利用,例如用作未支撐膜,且在其他具體實例中,多孔PTFE膜可與其他多孔元件及/或另一種組件組合,以提供例如物件,諸如複合物、過濾器元件及/或過濾器。
用於製備塗層之適合PFSA聚合物分散液之一個實例獲自Specialty Polymers(Borger,Texas)之Aquivion® PFSA(例如AQUIVION PFSA D83-24B、AQUIVION PFSA D83-06A及AQUIVION PFSA D79-20BS),其係基於四氟乙烯及磺醯氟乙烯基醚(Sulfonyl Fluoride Vinyl Ether;SFVE)F2C=CF-O-CF2-CF2-SO2F之短側鏈(Short Side Chain;SSC)共聚物。離聚物分散液含有其磺酸形式。適合之PFSA聚合物分散液之另一實例為DuPontTM Nafion® PFSA聚合物分散液。
在製備塗層中,塗佈溶液中之PFSA濃度可因不同應用而不同。典型地,濃度在約0.1%至約3%範圍內、更佳地在約0.12%至約2.2%範圍內。
多種多孔PTFE基板及膜(包括市售基板及膜)可根據本發明加以塗佈。
膜及基板可如本領域中已知來塗佈,例如(但不限於)浸塗或噴塗。
膜可具有任何適合之孔隙結構,例如孔隙尺寸(例如,如由起泡點或由如例如美國專利4,340,479中所描述之KL所證明,或由毛細冷凝流動式孔隙測定法(capillary condensation flow porometry)所證明)、平均流量孔隙(mean flow pore;MFP)尺寸(例如當使用例如Porvair孔率儀(Porvair plc,Norfolk,UK)之孔率儀,或以商標POROLUX(Porometer公司;Belgium)購得之孔率儀特性化時)、孔等級、孔直徑(例如當使用如例如美國專利4,925,572中所描述之經修改OSU F2測試特性化時),或可具有移除評定介質(removal rating media)。所用孔隙結構取決於待利用粒子之尺寸、待處理流體之組成、及所處理流體之所要流出水準。
典型地,根據本發明之經塗佈多孔PTFE膜的孔等級為約1微米或1微米以下、較佳(尤其用於非抗濕潤應用)在約0.05微米至約0.02微米或0.02以下範圍內。舉例而言,膜可為奈米多孔膜,例如孔隙直徑在1nm至100nm範圍內的膜。
典型地,經塗佈膜之厚度在約0.2至約5.0密耳(約5至約127微米)之範圍內、較佳地在約0.5至約1.0密耳(約13至約25微米)之
範圍內,然而膜可比彼等值厚或薄。
多孔膜可具有任何所需臨界潤濕表面張力(critical wetting surface tension;CWST,如在例如美國專利4,925,572中所定義)。CWST可藉由基於一組具有某些組成之溶液來量測。各溶液具有特定表面張力。溶液表面張力以較小的非相等增量介於25至92達因/公分範圍內。為量測膜表面張力,將膜置放於白光台之頂部上,將一滴具有某一表面張力之溶液塗覆於膜表面上,且記錄液滴滲透通過膜且變為亮白色(作為光穿過膜之指示)所花費之時間。當液滴滲透膜所花費之時間10秒時視為即刻潤濕。若時間>10秒,則溶液視為部分潤濕膜。可如此項技術中所知,例如如另外在例如美國專利5,152,905、5,443,743、5,472,621及6,074,869中所揭示來選擇CWST。
典型地,經塗佈PTFE膜之CWST為至少約27達因/公分(約27×10-5N/cm)、更佳地至少約30達因/公分(約30×10-5N/cm),且在一些具體實例中,為至少約35達因/公分(約35×10-5N/cm)。舉例而言,經塗佈PTFE膜之CWST可在約30達因/公分(約30×10-5N/cm)至約40達因/公分(約40×10-5N/cm)或40達因/公分以上之範圍內。
包括經塗佈多孔PTFE膜之物件,諸如過濾器、過濾器元件及/或複合物,可包括其他元件、層或組件,其可具有不同結構及/或功能,例如以下任何一或多者中之至少一者:預濾、載體、排泄、間隔及緩衝。說明性地,過濾器亦可包括至少一個其他元件,諸如網及/或篩。
根據本發明之具體實例,膜、過濾器元件、複合物及/或過濾器可具有多種組態,包括平面、摺疊、螺旋形及/或空心圓柱形。
膜、過濾器元件、複合物及/或過濾器典型地安置於外殼中,該外殼包含至少一個入口及至少一個出口,且在入口與出口之間界定至少一個流體流徑,其中該膜跨越流體流徑以提供過濾裝置。較佳地,就交叉流應用而言,膜、複合物及/或過濾器安置於外殼中,該外殼包含至少一個入口及至少兩個出口,且在入口與第一出口之間界定至少一個第一流體流徑及在入口與第二出口之間界定第二流體流徑,其中該膜跨越第一流體流徑以提供過濾裝置。過濾裝置可為可滅菌的。可採用具有適合形狀且提供至少一個入口及至少一個出口之任何外殼。
外殼可由任何適合的剛性不透水材料製造,該材料包括與處理中之流體相容的任何不透水熱塑性材料。舉例而言,可自諸如不鏽鋼之金屬或自聚合物製造外殼。在一具體實例中,外殼為聚合物,諸如丙烯酸、聚丙烯、聚苯乙烯或聚碳酸酯樹脂。
以下實施例進一步說明本發明,但當然不應解釋為以任何方式限制其範圍。
實施例1
此實施例展現製備根據本發明之一具體實例之膜的方法。
0.25% PFSA溶液(AQUIVION PFSA 24;D83-24B Solvay Plastics)在甲醇-水介質中製備,獲得聚合物溶液。將市售PTFE基板((膜)Sumitomo Electric Fine Polymer公司,平均孔隙尺寸50nm)用聚合物溶液浸漬塗佈直至完全潤濕為止,自溶液移除,且排液約2分鐘,且固定,且在150℃下乾燥10分鐘,接著在室溫DI水中洗滌12小時,且測試。
結果(與未經處理之(對照)PTFE膜及市售UV處理之PTFE
膜相比)如下:
根據本發明之一具體實例,此實施例展示CWST增加(因此,膜為非抗濕潤的),伴隨流量略微減小。
實施例2
此實施例展示與未經處理之(對照)PTFE膜及市售UV處理之PTFE膜相比,兩種根據本發明之具體實例之PFSA塗佈PTFE膜(用不同濃度之PFSA製備)的金屬移除效率。
兩種PFSA塗佈之PTFE膜如實施例1中大體上所描述來製備,其中一種膜在於甲醇-水介質中製備之0.25% PFSA溶液(AQUIVION PFSA D83-24B)中浸漬塗佈,且另一種膜在於甲醇-水介質中製備之0.5% PFSA溶液(AQUIVION PFSA D83-24B)中浸漬塗佈。
流體樣品分別含有以下金屬:Li、Na、K(第1族金屬);Mg、Ca(第2族金屬);Al、Pb(第3族金屬);及Cr、Mo、Mn、Fe、Ni、Cu、Zn(過渡金屬)。
如圖1中所展示,與未經處理之膜及市售UV處理之膜相比,根據本發明之膜之具體實例有效地移除多種第2族金屬及多種過渡金屬。
實施例3
此實施例展示兩種根據本發明之具體實例之PFSA塗佈PTFE膜(用不同濃度之PFSA製備)的金屬移除效率。
兩種PFSA塗佈之PTFE膜如實施例1中大體上所描述來製備,其中一種膜在於甲醇-水介質中製備之0.25% PFSA溶液(AQUIVION PFSA D83-24B)中浸漬塗佈,且另一種膜在於甲醇-水介質中製備之0.5% PFSA溶液(AQUIVION PFSA D83-24B)中浸漬塗佈。
流體樣品分別含有以下金屬:Li、Na、K(第1族金屬);Mg、Ca(第2族金屬);Al、Pb(第3族金屬);及Cr、Mo、Mn、Fe、Ni、Cu、Zn(過渡金屬)。
如圖2中所展示,與未經處理之膜相比,根據本發明之膜之具體實例更加有效地移除第2族金屬以及多種第3族金屬及多種過渡金屬,且展示吸收係歸因於塗佈而非篩分。
實施例4
此實施例展示PTFE膜上之PFSA塗層未交聯,因為塗層不藉由在溶劑中浸泡來移除。
PTFE膜使用7數位天平稱量。
膜使用24% w/w(儲備液)PFSA溶液如實施例1中大體上所描述來塗佈,得到非交聯膜。
交聯膜使用24% w/w(儲備液)PFSA溶液製備,其中膜在約260℃下乾燥。
稱量經乾燥之對照膜、非交聯膜及交聯膜。
將膜浸泡於用於製造經塗佈膜之相同溶劑(甲醇)溶液中。將一組經塗佈膜浸泡於室溫溶劑溶液中,另一組經塗佈膜浸泡於40℃溶劑溶液中。使用40℃溶劑溶液有助於加速任何副產物之溶合作用。
將膜在新鮮溶劑中沖洗3次,乾燥,且再次稱量。
在室溫及40℃溶劑溶液中浸泡之對照膜及非交聯經塗佈膜之重量與初始重量相同,而在室溫及40℃溶劑溶液中浸泡之交聯經塗佈膜之重量小於初始重量,由此展示膜為交聯的。
本文中所引用之所有參考文獻(包括公開案、專利申請案及專利)特此以引用之方式併入,該引用程度如同各參考文獻個別且特定地指示為以引用之方式併入且在本文中全文闡述一般。
除非本文中另外指示或與上下文明顯矛盾,否則在描述本發明之上下文中(尤其在以下申請專利範圍之上下文中)使用術語「一(a/an)」及「該」及「至少一個」及類似參照物應解釋為涵蓋單數及複數兩者。除非本文中另外指示或與上下文明顯矛盾,否則使用後接一或多個項目之清單(例如「A及B中之至少一者(at least one of A and B)」)之術語「至少一者(at least one)」應理解為意謂選自所列舉項目之一個項目(A或B)或所列舉項目中之兩者或兩者以上的任何組合(A及B)。除非另外說明,否則術語「包含(comprising)」、「具有(having)」、「包括(including)」及「含有(containing)」應理解為開放術語(亦即意謂「包括(但不限於)」)。除非本文另外指示,否則本文中數值範圍之列舉僅意欲充當個別提及屬於該範圍內之各獨立值之簡寫方法,且各獨立值併入本說明書中,如同在本文中個別敍述一般。除非本文中另外指示或另外上下文明顯矛盾,否則本文中
所描述之所有方法可以任何適合之次序進行。除非另外主張,否則使用本文所提供之任何及所有實例或例示性語言(例如,「諸如」)僅意欲較好地闡明本發明而不對本發明之範圍造成限制。本說明書中之語言不應理解為指示任何未主張之要素對於實踐本發明而言必不可少。
本發明之較佳具體實例描述於本文中,包括本發明人已知之進行本發明的最佳模式。在閱讀以上描述之後,彼等較佳具體實例之變化形式對於一般技術者可變得顯而易見。本發明人期望熟習此項技術者適當時採用此等變化形式,且本發明人意欲以不同於本文中特定所述之方式實踐本發明。相應地,若適用法律允許,則本發明包括在此隨附之申請專利範圍中所陳述之標的物的所有修改及等效物。此外,除非本文中另外指示或另外上下文明顯矛盾,否則本發明涵蓋上述要素以其所有可能變化形式之任何組合。
Claims (7)
- 一種用於過濾含金屬流體之方法,該方法包含使含金屬流體穿過包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,該PFSA聚合物包含AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS,其中該非交聯塗層係藉由以PFSA聚合物濃度在約0.1%至約3%範圍內的AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS聚合物溶液塗佈該多孔PTFE基板且將該AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS聚合物溶液固化所製備,以及該膜之CWST為至少約30達因/公分(約30×10-5N/cm)及孔等級為1nm至100nm,且將金屬自該流體移除。
- 一種用於過濾過氧化硫混合物(SPM)流體之方法,該方法包含使該流體穿過包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,該PFSA聚合物包含AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS,其中該非交聯塗層係藉由以PFSA聚合物濃度在約0.1%至約3%範圍內的AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS聚合物溶液塗佈該多孔PTFE基板且將該AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS聚合物溶液固化所製備,以及該膜之CWST為至少約30達因/公分(約30×10-5N/cm)及孔等級為1nm至100nm,且將粒子自該流體移除。
- 如申請專利範圍第1項或第2項之方法,其中該流體為用於電子工業之流體。
- 如申請專利範圍第1項或第2項之方法,其包含將第2族金屬及/或過渡金屬自該流體移除。
- 如申請專利範圍第3項之方法,其包含將第2族金屬及/或過渡金屬自該流體移除。
- 一種包含多孔PTFE基板之多孔PTFE膜,該多孔PTFE基板具有包含全氟磺酸(PFSA)聚合物之非交聯塗層,該PFSA聚合物包含AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS,其中該非交聯塗層係藉由以PFSA聚合物濃度在約0.1%至約3%範圍內的AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS聚合物溶液塗佈該多孔PTFE基板且將該AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS聚合物溶液固化所製備,以及該膜之CWST為至少約30達因/公分(約30×10-5N/cm)及孔等級為1nm至100nm。
- 一種製造如申請專利範圍第6項之金屬移除多孔PTFE膜之方法,該方法包含用包含全氟磺酸(PFSA)聚合物溶液之塗層塗佈多孔PTFE基板,該PFSA聚合物溶液包含AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS,且該AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS之PFSA聚合物濃度在約0.1%至約3%範圍內;且在低於約200℃之溫度下固化該AQUIVION® PFSA D83-24B或AQUIVION® PFSA D79-20BS聚合物溶液。
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US10322379B2 (en) * | 2014-07-21 | 2019-06-18 | Ohio State Innovation Foundation | Composite membranes for separation of gases |
US20170028361A1 (en) * | 2015-07-31 | 2017-02-02 | Pall Corporation | Ptfe/pfsa blended membrane |
WO2019181580A1 (ja) * | 2018-03-22 | 2019-09-26 | 富士フイルム株式会社 | ろ過装置、精製装置、薬液の製造方法 |
JP2022018727A (ja) * | 2020-07-16 | 2022-01-27 | 住友化学株式会社 | ガス分離膜及びその製造方法 |
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- 2016-05-19 EP EP16170377.2A patent/EP3130394B1/en active Active
- 2016-05-30 KR KR1020160066199A patent/KR20170015118A/ko not_active Application Discontinuation
- 2016-05-31 TW TW105117024A patent/TWI637988B/zh active
- 2016-05-31 CN CN201610555725.6A patent/CN106390778A/zh active Pending
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CN106390778A (zh) | 2017-02-15 |
SG10201603824PA (en) | 2017-02-27 |
JP2017029975A (ja) | 2017-02-09 |
EP3130394A1 (en) | 2017-02-15 |
US20170028359A1 (en) | 2017-02-02 |
JP6295456B2 (ja) | 2018-03-20 |
EP3130394B1 (en) | 2023-10-25 |
TW201704306A (zh) | 2017-02-01 |
KR20170015118A (ko) | 2017-02-08 |
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